Acid dyestuffs of the anthraquinone series and a process of preparing the same



Patented Nov. 28, 1933 E S T S PATENT. OFFICE :ACID DYESTI IFI' S 'OF THE ANTHRAQUIN- -ONE SERIES AND A PROCESS OF PREPAR- mc. THE SAME Georg Kraenzlein and-Ernst Diefenbach, Frankfort on-the-Main-Hochst, Germany, assignors to. General Aniline Works, Inc., New a corporation of Delaware No ,Drawing. Application January. 30, 1931, Serial No. 512,490, and in R1 occupies the ortho position to the CH2 group.

The benzene radicals-R and R1 may contain substituents, such as alkyl, OH, O-alkyl, halogen, COOH. Our new dyestuffs. which dye wooland silk blue tints of good fastness properties are obtainable with a good yield by condensing a- 1- amino-4-halogen-anthraquinone-2-sulfonic acid of the formula: I

or a salt thereof, witha compound of the for-- wherein R; and R1 represent radicals of the benzene series and the COOH group inthe radical R1 occupies the ortho-position to the CH2 group, or a salt thereof, by heating thecomponents in 'the presence "of an acid binding agent and" a small quantity of a copper compound.

The new compounds may be used as dyestuffs:

halogen-4-arylidoanthraquinoris thus Obtained the sulfonic acid group for the halogen atom alkali metal sulfites. 7 I V We have furthermore-found thatthe blue acid .dyestufis,'obtainable as above .described,-ma'y be Germany February.

,3 13 Claims. (01.260

' standing in 2-position of the anthraduinone compound;advantageously by; treatment with converted into newdyestuffshaving entirelydiie ferentproperties, by treating theniwith con-. centr'ated sulfuric acid or a; similar agent, such as chlorosulfonic acid. The conversion even oc--' curs under very mild conditions of reaction, especially at low temperatures.- The blue-dyestuifs used as starting materials chiefly yield brown to." gray to .greendyestuifs; The constitution of the new products has not yet been'definitely ascer-i tained, but most probably ring closurezoccurs by the dehydrating action ofthe sulfuric acid.

- Thefollowing examples serve to illustrate the invention but they are'not' intended to limit it thereto, theparts being'byweight unless stated otherwise:

'1'. 20 parts of .2" arnino-diphenylmethane-2- carboxylic acidobtainable by splitting up the lactam ofortho-aminobenzoyl benzoic acid,-pre pared according to the copendingfU. S. patent.

application Ser. No. 336,324 by "treating phthalic acid phenylimide in a melt of a mixture of'alumin ium chloride and sodiumchloride at a temperature of 285 C. to 290 0.; intothe orthoeaminov benzoyl benzoic acid and subsequent reduction; I colorless needles, melting at 135 C.-136 C.-are

dissolved, while gently heating, in,300 parts ofa 5% solution-of sodium carbonate. 24ypa-rts of, sodium' 1-amino-4-bromo-anthraquinone-2-sulf 'fonate and 1 part of finely powdered cuprous chloride are added. The mixture ifs-.heated to gentle boiling until the formation of the dyestuff is finished. v Thereupon; the dyestufiis precipi-s vtated by acidifying the solution with dilute.;hy- I I drochloric acid or by :salting itout by mearis 'of' sodium chloride. Inorder to purify the dye"- stuff, it is redissolved in a ,dilute' sodium carbonatesolution, repre'ci'pitated, washed with a 10% solutionof sodium chloride anddried'at 60 C. C. The dyestuflt is-thus obtained with a good yield in the form of small violets crystals having a metallic lustre. It dyes wooland silk beautiful blue'tints and dissolves incold con=-' centrate'd sulfuric acid to' a blue solution which, 7 after a short time, turns greenand finally passes to brownish-green. ,Whendiluting the sulfuric loo acid solution with water a brownish flaky precipitate is obtained.

2. 38 parts of]1-amino-2. l-dibromo-anthraquinone, parts of 2-aminodiphenylmethane-2 carboxylic acid, 20 parts of anhydrous potassium acetate, 0.5 part of copper acetate and 0.5 part of copper bronze are mixed with 400 parts :by volume of 'arn'yl alcohol, and the whole is heated in an autoclave for 20 hours at 150..C.., While stirring. After cooling, the condensation prodwashed with alcohol and water-andjdried In order to convert the v co nden'sat'i'on ior-oduct into the sulfonic acid, 15 parts of the crude condensation product are heated to gentle boiling with 60 ars of henol, 1 2 ars or otassiurn p 0 p p b p solved :1'11 asolution of 22 parts ofv sodium carbosulfite and parts of waternntil the jdye'stufi has become entirely soluble in water. The phem1 is removed by steam-distillation, the solution is filtered and the reaction-product is' pre cipitated from the filtrate by acidifying. It is identical with the dyestuif described ple1..

3. l partof the product obtainable by condens'ation or 1 -amino-4-bromo-anthraquinone-2ssule in Examfonic acid with 2'-aminosdiphenylmethane 2- (described in',.;Example l) carboxylic acid is'dissolved ina finely powdered state in 10 parts of concentratedsulfuric acid, while stirring andv maintaining a temperature 5 C.,l0 C. The color of the'solutionwhich'is at first blue, after a s'hort timeppasscs to green anclfinally t0 brownish green. ilvhile well stirring, the solution is poured intoicold water, the dyestufflwhich precipitatesin brown flakes is filtered with suction, and washed with a 10% solution .of sodium chloride until neutral. The. dry dyestuff tormsxa brown powder" which easily dissolves in water .to

4 an intense reddish brown solution and dyes wool and silkbeautiful brown tints. r Q

parts 'of e-amino-diphenylmethanezacarboxylic acid-obtaina'ble by causing d-chlorobenzoyl-ortho-benzoic"acid .to react with ammonia according to German Patent No. 234,917 and subsequent reduction; nearly colorless brilliant' needles, melting at 174 C.l- C.-+dissolved" in 7 50 parts of water and 88 parts of sodium carbonate, "are mixedfwith 60 parts of sodium l-amino-4-#bromoanthraqu-inone+2= sulfonate and 2.5 parts of .cu-prous chloride. Ail-'1 ready atter half anhours gentle "boiling the.

mixtureassumesa pure blue coloration and is heatedjio r further .6 hours under reflux in order to terminate the condensation. The .dyestuif is isolated and purified according to one of the.

usuali'nethods and forms a blue'crystalline powder. It dyes wool and silk clear pure greenish blue t nts;

5, l partof the dyestuff obtainable from- 4' arm o diphenyImethane- Z carboxylic acid, de-- scribedin Example 4, isintro'duced into 10 parts qt oncentrated sulfuric acid. It dissolves with a uecoloration which, after stirring for ashort time turn o e h tempe ature is g ad a y raised i050" 603 whereby the color of the solution passes to bluish-green with evolution oi. $02.; The solution is poured intowa'ter, filtered with suction,v and the solid matter iswashed with a dilute solution ofsodium chloride until.

neutral and dried. There is obtained a black powder having a metallic lustre, dissolving in hot water to ablu'e solution and dyeing wool and silk from an acid bath gray to deep black tints.

'6. 20 parts of the product obtainable by condensation of 1-amino-4-bromo-anthraquinone-2- sulfonic acid with 4-amino-diphenylmethane- 2-carb0xylic acid, described in Example 4, are dissolved in 200 parts of chlorosulfonic acid and stirred for 20 hours at 15 C. The temperature is then raised to 50 C. in the course of hour, the solution is poured into .cold water, the dye stuff which has separated is filtered with suction and washed first with water and then with a 10%solution of sodium chlorideuntil'neutral uct which has separated, is filteredwith suction, dried" The dyestuff dyes W001 and silk -na-te-in500 parts'of-water and 40 parts of sodium- 1 aminol bromo-anthraquinone 2 sulfonate and l. .partofcuprous chloride are added thereto. Aitengentle boiling under reflux for 12 hours the condensation finished. The dyestuff is isolated and purified by one of the usual methods. 'It'forms a dark blue powder, dissolving in water to a blue solution, -and .dyes wool and silk .clear blue tints. i

8. The blue dyestufi obtainable from .3 aminodiphenylmethane 4C2=dicarboxylic acid, .described in Example '7 is dissolved in 10 times its Weight of concentrated sulfuric acid at 5 C.10 0., while stirring. The color of the solution is at first green and gradually turns violetish brown. By pouring the solution into water, the dyestuff precipitates in the formof green fiakes. It is filtered with suction and washed with cold water until neutral; it forms a dark powder which dissolves in water to a green solution and dyes wool and silk bluish green tints. d

9. 8 parts of 2'-amino4'-chloro-diphenyl methane-Z-carboxylic acid'obtainable by splitting up the la'ctamj of 2-amino-4-chlorbenzoylortho-benzoic acid, prepared-accordingto the copending U. S. application Ser. No. 336,324 'by' I treating phthalic acidemwhlorophenylimide in a melt of a mixture of aluminium chloride and sodium chloride at a temperature of 300 C. to 310 (2., and subsequent reduction of the CO.

group-are heated to gentle boiling for 20 hours 1 The reaction product is isolated and purified by'one of the usual methods. It forms a dark blue powder having ametallic lustre and dis-.

solves in water to a blue solution. It dissolves in concentrated sulfuric acid to a'blue-green so-fl lution which, after a short time, turns green and finally passes to brown. By very 'much diluting the sulfuric acid solution with water, brownv flakes precipitate. V

- l0. The blue dyestufi, obtainable fromf2 amino-4- chloro diphenylmethane -Z-carboxylic acid and described in Example 9, is treated with concentrated sulfuric acid as indicated in Example 3. Thereby the color of theisolution which is at first blue green, after a shorttime, turns green and finally passes to brown and the reac: tion productprecipitates, on dilution with water, 1

brown tints.

We claim:

1. As a new product, the acid dyestuff of the v following constitution:

forming small violet crystals of a metallic lustre,

dissolving in cold concentrated sulfuric acid to a blue solution, dyeing wool and silk beautiful blue tints.

, 2. As a new product, the acid dyestuff of the following constitution:

I ing formula:

forming a blue crystalline powder, dyeing wool and silk clear pure greenish-blue tints.

3. As a new product, the acid dyestuff of V the following constitution:

forming a dark-blue powder which dissolves in 2 water to a blue solution and dyeing wool and silk clear blue tints.

4. As new products, the acid dyestuffs obtainable by causing a compound of the formula:

compound of thefollowinggeneral formula:

wool andsilk chiefly brown to grey to greenish tints.

'wooland silk grayish todeep-black tints.*-

e 1 5. As a new product, the 'acid dyestufi obtain able by causing concentrated sulfuric acid toact at 5 C.-10 C. upon acompound of the following I formula: I v

forming a'brown powder, easily solublein water; dyeing wool and silk beautiful brown tints.

6. As a new product, means dyestuff'obtain able by causing concentrated sulfuric acid to act at 50 C.-60 C. upon a'compound of the followforming a dark powder of a metallic lustre, which dissolvesinwater'to a blue solution, and dyeing 7. As a new-product; the acid dyestufi bt inzi able by causing concentrated sulfuric'acidjtojact, 1:15 at 5 C.-10 C. upon a compound of the following forming a dark powder, which'dissolyes in water to a green solution, dyeing wool and silk bluish 1 f v green tints. wherein Z stands for OH or Cl toa'ct upon a- 8. Theprocess which comprises condensing a compound'of the following formula:

i? NIH: I

scan

0 halogen with a compound of the following formula! 'H2N-RCHz-R1COOH wherein R and R1 7 represent radicals of the benzene series and 3'3".

the COOH group in the radical R1 occupies'the' ortho-position to the CH2 group, by heating the components. in the presence" of an acid binding agent and a small quantity of a copper compound. V

ass

9. The process :which'icomprisescondensing a compound of the following-formula; Y

' c r'NHa 'sogoNa with a compound of the following formula:

NH: COOH by heating the components in the presence of Water, sodium carbonate and a small quantity of cuprouschloride. r v

10. The process which comprises condensing a compound of the following formula:

i .NH

SOzONa I 0 Br with a compound of the following formula:

COOH i loyheating the components in thepresenceofwater, sodium carbonate and a small quantity of cuprous chloride 7 a s 11.]Ihe process which comprises condensing a'compound of the following formula:

esa-944% with a compound of the following formula: NH1 000s;

by heating the components in the presence of water, sodium acetate and a small quantity of cuprous chloride.

12. The process which comprises causing a compound of the formula:,

R-'omR1oooH wherein R and R1 represent radicals of the benzene series and the COOH group in the radical R1 occupies the" ortho-position to the CH2 group, under mild conditions, particularly with regard to the reaction temperature. V

13. As new products, the acid dyestuffs of the following general formula:

wherein 'R and R1 represent radicals of the benzene series andthe COOH group in the radical R1 occupies the ortho-position'to the CH2 group, 0 dyeing wool andsilk blue tints of good fastness properties. v

- GEORG KRAENZLEIN.

ERNST DIEFENBACH. 

